Composite powder, preparation and use thereof

ABSTRACT

The present invention relates to a composite powder, preparation and use thereof. The composite powder according to the present invention is prepared by intimately mixing an irradiated or non-irradiated rubber latex with a slurry of inorganic particles in a ratio corresponding to that of rubber particles to inorganic particles in the composite powder according to the present invention, and then drying the resultant mixture. The composite powder according to the present invention comprises agglomerates composed of powdery rubber particles and inorganic particles, with inorganic particles being uniformly distributed either inside the agglomerats or both inside the agglomerates and on the surfaces thereof. The composite powder according to the present invention can be easily dispersed in plastic matrixes and thus can be compounded with plastics to produce toughened plastics and thermoplastic elastomers.

FIELD OF THE INVENTION

The present invention relates to a powder, more particularly, to acomposite powder comprising rubber particles and inorganic particles,preparation and use thereof.

BACKGROUND OF THE INVENTION

The International Patent Publication WO 01/40356A1 (filed on Sep. 18,2000, claiming the benefit of the Chinese Patent Application No.99125530.5 filed by the present applicants on Dec. 3, 1999) discloses afully vulcanized powdery rubber, which means discrete, fine rubberpowders having a gel content of 60 percent by weight or more and freelyflowing after drying without any partitioning agents. Such powderyrubbers are obtained by irradiating a rubber latex in the absence orpresence of a cross-linking agent so as to cross-link them and fix theparticle size of the rubber particles, and then subjecting theirradiated latex to precipitation or spray drying. The fully vulcanizedpowdery rubber thus obtained has a particle size in the range of from 20to 2000 nm and can be used as tougheners for plastics, with excellenttoughening effects being achieved. However, when such a powdery rubberis used for toughening plastics, the strength, modulus and thermalproperties inherent in the plastics are frequently reduced.

Since 1980s, inorganic particles have been proposed for modifyingplastics. However, inorganic particles have a very high surface energy,thus if no special treatment is conducted, they are apt to agglomeratewhen blending with plastics, which will significantly decrease theirmodification effects on plastics. For example, nano-clay materials arenow being used for enhancing the rigidity of polyamides, withpolyamide/clay nano-composites being obtained (see, for example,“Polymers-Inorganics Nano-composites”, Series of Nano-materials andApplication Technologies, the Chemical and Industrial Press, December,2002). The clays used for preparing polyamide/clay nano-composites areconventionally sheet clays, which possess a layered structure in ananometric scale, are natural nano-materials and are very suitable forpreparing nano-composites. However, the gaps among the layers of thesheet clays are very small, thus it is impossible for organic polymersto enter said gaps to exfoliate the sheet clays in a nanometric scale.Therefore, before used for preparing such polymer/clay nano-composites,clays must be subjected to a special treatment, i.e., displacement byvarious organic substances, thereby obtaining nano-precursor materialscontaining organic functional groups, which are then compounded withpolymers to form nano-composites. The process for preparing suchnano-precursor materials is also called organo-modification of clays.After such an organo-modification, organic functional groups, such asorganic cations and the like, are introduced to the gaps of the sheetclays, which facilitates the insertion of monomers or polymers (see, forexample, “Polymer-Inorganics Nano-composites”, pp. 21-22). Byintercalation-compounding, the layers of sheet clays subjected toorgano-modification can be dispersed in polymer matrix in a nanometricscale, thereby obtaining polymer/clay nano-composites, which possesshigh strength, modulus, heat distortion temperature. Theorgano-modification of montmorillonite facilitates theintercalation-compounding and however, renders the preparation ofcomposites complicated.

DISCLOSURE OF THE INVENTION

In view of the above, the present inventors conducted extensive andintensive researches in the field of toughening plastics, with a view ofdeveloping a novel toughener which can be used to toughen plastics andmeanwhile, retains the strength, modulus and thermal properties inherentin plastics. As a result of many experiments, the present inventorsfound that by compounding powdery rubbers with inorganic particles, acomposite powder comprising organic elastic particles and inorganicrigid particles can be obtained, and when blending with plastics, theorganic elastic particles contained in such a composite powder preventthe agglomeration of inorganic particles, thus a better tougheningeffect can be achieved by toughening plastics with such a compositepowder, compared to using elastic particles or inorganic particlesalone, and meanwhile, the negative effects on rigidity and heatresistance of resins caused by the introduction of elastic particles arereduced. Furthermore, such a composite powder can be advantageously usedfor the preparation of thermoplastic elastomers.

Therefore, an object of the present invention is to provide a compositepowder, which can be used for toughening plastics and for preparingthermoplastic elastomers.

Another object of the present invention is to provide a process forpreparing the composite powder according to the present invention.

Still another object of the present invention is to provide use of thecomposite powder according to the present invention for preparingtoughened plastics and thermoplastic elastomers.

The present invention in its one aspect provides a composite powder,comprising powdery rubber particles having a cross-linked structure andinorganic particles distributed between said rubber particles.

The present invention in its second aspect provides a process forpreparing the composite powder according to the present invention,comprising intimately mixing an irradiated or non-irradiated rubberlatex with a slurry of inorganic particles in a ratio corresponding tothat of rubber particles to inorganic particles in the composite powderaccording to the present invention, and then drying the resultantmixture.

The present invention in its third aspect provides plastics toughened bythe composite powder according to the present invention.

The present invention in its fourth aspect provides thermoplasticelastomers comprising the composite powder according to the presentinvention.

These and other objects, features and advantages of the presentinvention will be apparent after reading the whole description inconjunction with the drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a transmission electron micrograph of the sample obtained inExample 15, in which the shadow stands for agglomerates composed ofrubber particles and inorganic particles, which are dispersed in theplastic matrix, with the darker spots in the shadow being inorganicparticles dispersed in agglomerated rubber particles.

FIG. 2 is a transmission electron micrograph of the sample obtained inExample 17, in which the shadow stands for agglomerates composed ofrubber particles and inorganic particles, which are dispersed in theplastic matrix, with the darker spots in the shadow being inorganicparticles dispersed in agglomerated rubber particles.

FIG. 3 is a transmission electron micrograph of the sample obtained inExample 14, in which the circular shadow stands forbutadiene-styrene-vinylpyridine rubber particles and the strip-shapedshadow stands for sodium-based montmorillonite, with the rubberparticles and montmorillonite being uniformly dispersed in the polyamidematrix and at the same time, the sheet montmorillonite being completelyexfoliated in the matrix.

DETAILED DESCRIPTION OF THE INVENTION

The composite powder according to the present invention comprisespowdery rubber particles having a cross-linked structure and inorganicparticles distributed between said rubber particles, wherein the weightratio of said rubber particles to said inorganic particles is from99.5:0.5 to 20:80, preferably from 99:1 to 50:50.

In the composite powder according to the present invention, theinorganic particles are those commercially available in the prior art.There are no restrictions on the type of the inorganic particles as longas the size thereof falls within the scope of the present invention.However, the inorganic particles which are unstable when encounteringwater are excluded. The inorganic particles can be of any shape, such asspheres, ellipsoids, sheets, needles or irregular shapes. In the view ofthree-dimensional point, the individual particles have an average sizeof from 0.2 to 500 nm, preferably from 0.5 to 100 nm in at least onedimension.

The inorganic particles used in the composite powder according to thepresent invention can be selected from elemental metals or alloysthereof, such as gold, silver, copper, iron or alloys thereof; metaloxides, such as aluminum oxide (Al₂O₃), magnesium oxide (MgO), titaniumdioxide (TiO₂), iron sesquioxide (Fe₂O₃), ferroferric oxide (Fe₃O₄),silver oxide (Ag₂O), zinc oxide (ZnO) and the like; metal or non-metalnitrides, such as aluminum nitride (AlN), silicon nitride (SiN₄) and thelike; non-metal carbides, such as silicon carbide (SiC) and the like;non-metal oxides, such as silicon dioxide (SiO₂) and the like; metalhydroxides, such as aluminum hydroxide (Al(OH)₃), magnesium hydroxide(Mg(OH)₂) and the like; metal salts, including metal carbonates,silicates, sulfates and the like, such as calcium carbonate (CaCO₃),barium sulfate (BaSO₄), calcium sulfate (CaSO₄), silver chloride (AgCl)and the like; mineral earths, such as asbestos, talc, kaolin, mica,feldspar, wollastonite, montmorillonite and the like; and the mixturesof two or more of them.

The powdery rubber particles having a cross-linked structure used in thecomposite powder according to the present invention are those having ahomogeneous structure, that is to say, individual particles arehomogeneous in their composition and no heterogeneous phenomena, such asdemixing, phase separation or the like can be observed in the particlesby current microscopic technologies. In addition, the powdery rubberparticles have a gel content of 60 percent by weight or more, preferably75 percent by weight or more, more preferably 80 percent by weight ormore.

The composite powder according to the present invention can be preparedby the process for preparing fully vulcanized powdery rubbers disclosedin the International Patent Publication WO 01/40356A1 filed by thepresent applicants on Sep. 18, 2000 (its full text is incorporatedherein by reference), except that the irradiated latex is admixed with aslurry of inorganic particles prior to drying.

In addition, the composite powder according to the present invention canalso be prepared by the process for preparing powdery cross-linkedrubbers disclosed in Chinese Patent Application No. 00130386.4 filed bythe present applicants on Nov. 3, 2000 (CN 1353131A, its full text isincorporated herein by reference), except that cross-linked rubberlatexes are admixed with a slurry of inorganic particles prior todrying.

The composite powder according to the present invention can optionallycomprise water-soluble nucleating agents for plastics and if such agentsare present, the amount thereof is such that the weight ratio of therubber particles to the nucleating agent in the composite powderaccording to the present invention is from 99:1 to 50:50, preferablyfrom 97:3 to 70:30. The nucleating agent can be those conventionallyemployed in the art, preferably sodium benzoate.

The composite powder according to the present invention comprisesagglomerates composed of powdery rubber particles and inorganicparticles, with inorganic particles being uniformly distributed eitherinside the agglomerate or both inside the agglomerates and on thesurfaces thereof, wherein the rubber particles themselves have a gelcontent of 60 percent by weight or more, preferably 75 percent by weightor more, more preferably 80 percent by weight or more. In addition tothe agglomerates composed of powdery rubber particles and inorganicparticles, the composite powder according to the present invention maycontain discrete inorganic particles. Especially when the content of theinorganic particles is high, inorganic particles are apt to occuroutside the agglomerates.

The agglomerating state possessed by the composite powder according tothe present invention can be retained in the composition obtained bymelt-blending the composite powder with non-polar plastics (such aspolypropylenes or polyethylenes). By subjecting the composition tomicrotoming and then observing under a transmission electron microscope,a photograph reflecting such an agglomerating state can be obtained (seeFIG. 1).

The composite powder according to the present invention can be preparedby intimately mixing an irradiated or non-irradiated rubber latex with aslurry of inorganic particles in a ratio corresponding to that of rubberparticles to inorganic particles in the composite powder according tothe present invention, and then drying the resultant mixture.

More particularly, the composite powder according to the presentinvention can be prepared by:

-   -   a. intimately mixing a slurry of inorganic particles with a        cross-linked synthetic rubber latex to obtain a mixed latex and        then drying the mixed latex; or    -   b. vulcanizing a rubber latex by high-energy irradiation in the        absence or presence of a cross-linking agent, intimately mixing        a slurry of inorganic particles with the irradiated rubber latex        to obtain a mixed latex and then drying the mixed latex.

In the process for preparing the composite powder according to thepresent invention, the slurry of inorganic particles is an aqueoussuspension of inorganic particles and can be commercially availableslurries. However, prior to mixing with rubber latexes, the commerciallyavailable slurries are normally dispersed by means of a conventionaldispersing equipment (such as a high-shear dispersing and emulsifyingmachine, colloidal mill and the like) so as to ensure that the solidparticles in the slurries can be homogeneously dispersed in water. Ifthe slurry of inorganic particles are not commercially available, theycan be prepared by dispersing inorganic particles in a suitable amountof water by means of conventional dispersing equipments to form a stablesuspension, which is then mixed with a rubber latex.

In the process for preparing the composite powder according to thepresent invention, the inorganic particles are those commerciallyavailable in the art. There are no restrictions on the type of theinorganic particles as long as the size thereof falls within the scopeof the present invention. However, the inorganic particles which areunstable when encountering water are excluded. The inorganic particlescan be of any shape, such as spheres, ellipsoids, sheets, needles orirregular shapes. In the view of three-dimensional point, the individualparticles have an average size of from 0.2 to 500 nm, preferably from0.5 to 100 nm in at least one dimension.

The inorganic particles used in the process according to the presentinvention can be selected from elemental metals or alloys thereof, suchas gold, silver, copper, iron or alloys thereof; metal oxides, such asaluminum oxide (Al₂O₃), magnesium oxide (MgO), titanium dioxide (TiO₂),iron sesquioxide (Fe₂O₃), ferroferric oxide (Fe₃O₄), silver oxide(Ag₂O), zinc oxide (ZnO) and the like; metal or non-metal nitrides, suchas aluminum nitride (AlN), silicon nitride (SiN₄) and the like;non-metal carbides, such as silicon carbide (SiC) and the like;non-metal oxides, such as silicon dioxide (SiO₂) and the like; metalhydroxides, such as aluminum hydroxide (Al(OH)₃), magnesium hydroxide(Mg(OH)₂) and the like; metal salts, including metal carbonates,silicates, sulfates and the like, such as calcium carbonate (CaCO₃),barium sulfate (BaSO₄), calcium sulfate (CaSO₄), silver chloride (AgCl)and the like; mineral earths, such as asbestos, talc, kaolin, mica,feldspar, wollastonite, montmorillonite and the like; and the mixturesof two or more of them.

In the process for preparing the composite powder according to thepresent invention, the ratio of the weight of the rubber contained inthe rubber latex (i.e., dry weight or solid content of the rubber latex)to the weight of the inorganic particles contained in the slurry ofinorganic particles (i.e., dry weight of the slurry of inorganicparticles) is from 99.5:0.5 to 20:80, preferably from 99:1 to 50:50.

In the process variant a. or b. for preparing the composite powderaccording to the present invention, the mixed latex can be obtained byintimately mixing a slurry of inorganic particles, an aqueous solutionof water-soluble nucleating agent for plastics and the irradiated rubberlatex (in the process variant b.) or the cross-linked rubber latex (inthe process variant a.). The ratio of the dry weight of the irradiatedrubber latex or the cross-linked rubber latex to the weight of thenucleating agent contained in the aqueous nucleating agent solution isfrom 99:1 to 50:50, preferably from 97:3 to 70:30. The composite powderthus obtained can improve the tougheness of plastics and at the sametime, promote the crystallization of crystalline plastics, which resultsin further improvement in the rigidity of plastics. In the processaccording to the present invention, there is no restriction on thewater-soluble nucleating agent for plastics as long as it iswater-soluble and promotes the nucleation of plastics. Sodium benzoateis preferably used.

In the process for preparing the composite powder according to thepresent invention, it is possible to add the slurry of inorganicparticles and optionally, an aqueous solution of water-solublenucleating agent for plastics to the irradiated rubber latex or thecross-linked rubber latex while stirring so as to intimately mix them.There are no particular restrictions on the concentrations of the rubberlatex, the slurry of inorganic particles and the aqueous nucleatingagent solution. The drying can be carried out by using the drying methodfor preparing the fully vulcanized powdery rubber disclosed in theInternational Patent Publication WO 01/40356A1 and the InternationalPatent Publication WO 01/98395 (filed on Jun. 15, 2001, claiming thebenefit of the Chinese Patent Application No. 00109217.0 filed by thepresent applicants on Jun. 15, 2000), that is to say, the drying can becarried out by means of a spray dryer, with the inlet temperature andthe outlet temperature being controlled to be 100 to 200° C. and 20 to80° C., respectively. The rubbers contained the composite powdersobtained by using the above process variants a. and b. has a gel contentequal to that in the cross-linked synthetic rubber latex in processvariant a. and that in the irradiated rubber latex in process variantb., respectively.

After a series of experiments, the present inventors found that somerubber latexes undergo a certain degree of cross-linking between therubber molecules during their synthesis, which results in rubber latexeshaving a certain degree of cross-linking. Such rubber latexes arereferred to as cross-linked rubber latexes. The Chinese PatentApplication No. 00130386.4 (CN 1353131A) filed by the present applicantson Nov. 3, 2000 mentioned such a cross-linked synthetic rubber latex,which has a gel content of 80 percent by weight or more, preferably 85percent by weight or more. Such a rubber latex is per se cross-linked toa higher degree, and thus can be directly spray dried to obtain powderyrubbers, without further irradiation cross-linking. In the processvariant a. for preparing the composite powder according to the presentinvention, such cross-linked synthetic rubber latexes are used as thestarting materials. Cross-linked synthetic rubber latexes can beselected from the group consisting of cross-linked styrene-butadienelatex, cross-linked carboxylated styrene-butadiene latex, cross-linkedpolybutadiene latex, cross-linked acrylonitrile-butadiene latex,cross-linked carboxylated acrylonitrile-butadiene latex, cross-linkedneoprene latex and cross-linked acrylic latex.

In the process variant b. for preparing the composite powder accordingto the present invention, there are no restrictions on the rubberlatexes as the starting materials. For example, they can be rubberlatexes used for preparing the fully vulcanized powdery rubbers in theInternational Patent Publications WO 01/40356A1 and WO 01/98395, such asnatural rubber latex, styrene-butadiene rubber latex, carboxylatedstyrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex,carboxylated acrylonitrile-butadiene rubber latex, polybutadiene rubberlatex, neoprene rubber latex, silicone rubber latex, acrylic rubberlatex, butadiene-styrene-vinylpyridine rubber latex, isoprene rubberlatex, butyl rubber latex, ethylene-proplyene rubber latex, polysulfiderubber latex, acrylate-butadiene rubber latex, urethane rubber latex,fluorine rubber latex and the like.

The rubber latexes used in the process variant b. for preparing thecomposite powder according to the present invention can also include thecross-linked synthetic rubber latexes used in the process variant a.,that is to say, the cross-linked synthetic rubber latexes can be used toprepare the composite powder according to the present invention withoutirradiation (as in the process variant a.) or with irradiation (as inthe process variant b.), with the gel content of the rubber in thecomposite powder obtained by the process variant b. being higher thanthat by the process variant a.

There are no particular restrictions on the solid content (i.e., dryweight) of the rubber latexes used in the above two process variants,which is normally from 20 to 70 percent by weight, preferably from 30 to60 percent by weight, more preferably from 40 to 50 percent by weight.The average particle size of the rubber particles in these rubberlatexes is from 20 to 2000 nm, preferably from 30 to 1500 nm, morepreferably from 50 to 500 nm. After irradiating the rubber latexes, therubber particles contained therein acquire a relatively high gel content(60 percent by weight or more), or in the case of the cross-linkedsynthetic rubber latexes, the particle size of the rubber particles isfixed due to the high gel content, thus after co-spraying the rubberlatex and the slurry of inorganic particles, the particle size ofindividual rubber particles is consistent with that of the rubberparticles contained in the rubber latexes as the starting material,i.e., from 20 to 2000 nm, preferably from 30 to 1500 nm, more preferablyfrom 50 to 500 nm, irrespective as of whether the rubber particles arein the form of agglomerates or in free state.

In the process variant b. for preparing the composite powder accordingto the present invention, the conditions for irradiating rubber latexes,including cross-linking agents, irradiation doses, sources ofhigh-energy irradiation and the like, are same as those in the processfor preparing fully vulcanized powdery rubbers disclosed in theInternational Patent Publications WO 01/40356A1 and WO 01/98395. Duringthe irradiation of rubber latexes, a cross-linking agent is optionallyused. The cross-linking agent used can be selected from the groupconsisting of mono-, di-, tri-, tetra- or multi-functional cross-linkingagents, and any combination thereof. Examples of monofunctionalcross-linking agents include, but not limited to, octyl(meth)acrylate,iso-octyl(meth)acrylate, glycidyl(meth)acrylate; examples ofdifunctional cross-linking agents include, but not limited to,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,neopentyl glycol di(meth)acrylate, divinylbenzene; examples oftrifunctional cross-linking agents include, but not limited to,trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate;examples of tetrafunctional cross-linking agents include, but notlimited to pentaerythritol tetra(meth)acrylate, ethoxylatedpentaerythritol tetra(meth)acrylate; examples of multi-functionalcross-linking agents include, but not limited to dipentaerythritolpenta(meth)acrylate. In the context of the present application, the term“(meth)acrylate” means acrylate or methacrylate. These cross-linkingagents can be used alone or in any combination, as long as theyfacilitate the vulcanization under irradiation.

The amount of the cross-linking agent added varies depending on the typeand formulation of the rubber latexes, and is generally from 0.1 to 10percent by weight, preferably from 0.5 to 9 percent by weight, morepreferably from 0.7 to 7 percent by weight, based on the dry weight ofthe latexes.

In the process variant b. for preparing the composite powder accordingto the present invention, the high-energy irradiation which can be usedis selected from the group consisting of cobalt sources (such as Co-60),UV ray sources and high-energy electron accelerators, preferably cobaltsources. The irradiation dose can be from 0.1 to 30 Mrad, preferablyfrom 0.5 to 20 Mrad. The irradiation dose depends on the type andformulation of the rubber latexes. Generally, the irradiation dose issuch that the rubber latexes after vulcanization under irradiation havea gel content of 60 percent by weight or more, preferably 75 percent byweight, more preferably 80 percent by weight or more.

The composite powder according to the present invention, prepared byco-spraying the rubber latexes, the slurry of inorganic particles andthe like, comprises agglomerates composed of powdery rubber particlesand inorganic particles, with inorganic particles being uniformlydistributed either inside the agglomerate or both inside theagglomerates and on the surfaces thereof, wherein the rubber particlesthemselves have a gel content of 60 percent by weight or more,preferably 75 percent by weight or more, more preferably 80 percent byweight or more. In addition to the agglomerates composed of powderyrubber particles and inorganic particles, the composite powder accordingto the present invention may contain discrete inorganic particles.Especially when the content of the inorganic particles is high,inorganic particles are apt to occur outside the agglomerates.

The agglomerating state possessed by the composite powder according tothe present invention can be retained in the composition obtained bymelt-blending the composite powder with non-polar plastics (such aspolypropylenes or polyethylenes). By subjecting the composition tomicrotoming and then observing under a transmission electron microscope,a photograph reflecting such an agglomerating state can be obtained (seeFIG. 1).

The composite powder according to the present invention can be dispersedin plastic matrixes by conventional blending processes, wherein therubber particles facilitate the uniform dispersion of inorganicparticles in the matrix and thus the agglomeration of inorganicparticles is substantially avoided. In non-polar resin matrixes (such aspolypropylene or polyethylene), inorganic particles are uniformlydistributed in the agglomerates composed of inorganic particles andrubber particles, which results in a good modification effect. In thecase of resin matrixes which chemically react with the rubber particlesin the interface or have a large interaction with the rubber particlesin the interface, the rubber particles contained in the composite powderaccording to the present invention can be dispersed in the resinmatrixes in the form of individual particles after melt-blending, anddue to the fact that the inorganic particles contained in the compositepowder are uniformly dispersed between the rubber particles, the idealdispersion of the rubber particles in the resin facilitates thedispersion of inorganic particles. For example, in the case of layeredinorganic particles like montmorillonite, by preparing a compositepowder comprising montmorillonite particles and rubber particles,montmorillonite can be dispersed in polar resin matrixes like nylons inan exfoliated state by the action of rubber particles (as shown in FIG.3), without the complicated organo-modification.

The process for preparing the composite powder according to the presentinvention is simple, convenient and easy to carry out. When thecomposite powder according to the present invention is used fortoughening plastics, a better toughening effect can be achieved,compared to using rubber elastic particles alone, and meanwhile, thenegative effects on rigidity and heat resistance of resins caused by theintroduction of elastic particles are reduced. Furthermore, thecomposite powder according to the present invention can beadvantageously used for the preparation of thermoplastic elastomers.

The composite powder according to the present invention can be dispersedin plastics very easily, thus can be mixed with various plastics toprepare a number of toughened plastics and thermoplastic elastomers. Thepreparation of toughened plastics or thermoplastic elastomers can becarried out by simply mixing the composite powder according to thepresent invention and plastics in a certain proportion in conventionalblending equipments under conventional processing conditions, ifnecessary, in the presence of conventional processing aids andcompatilizers.

In the preparation of toughened plastics, the weight ratio of thecomposite powder according to the present invention to plastics is from0.5:99.5 to 50:50, preferably from 1:99 to 30:70. The plastics to betoughened can be nylons, polypropylenes, polyethylenes, polyvinylchloride, polyurethanes, polyesters, polycarbonates, polyoxymethylene,polystyrene, polyphenylene oxide (PPO), polyphenylene sulfide (PPS),polyimides, polysulfones, epoxy resins, unsaturated polyesters, phenolicresins, amino resins, alkyd resins, diallyl phthalate resins, siliconeresins or blends or mixtures thereof.

In the preparation of thermoplastic elastomers, the weight ratio of thecomposite powder according to the present invention to plastics is from30:70 to 75:25, preferably from 50:50 to 70:30. The plastics which canbe used are nylons, polypropylenes, polyethylenes, polyvinyl chloride,polyurethanes, polyesters, polycarbonates, polyoxymethylene,polystyrene, polyphenylene oxide (PPO), polyphenylene sulfide (PPS),polyimides, polysulfones, epoxy resins, unsaturated polyesters, phenolicresins, amino resins, alkyd resins, diallyl phthalate resins, siliconeresins or blends or mixtures thereof.

EXAMPLES

The present invention is further described with reference to thefollowing examples, which shall not be construed as limiting the presentinvention in any way. The scope of the present invention will be definedin the appended claims.

Testing and Characterizing Method of the Morphology of the CompositePowder:

The composite powder, propylene homopolymer powder or pellets (meltindex: <5 g/10 min) and an antioxidant (Irganox 1010, Ciba-Geigy) arecompounded at a weight ratio of the composite powder:polypropylene:1010of 100:10:0.5 in a high speed stirrer for 1 minute. The blending andpelleting are carried out in a ZSK-25 twin-screw extruder (Werner &Pfleiderer Co., Germany), with the temperatures for each section of theextruder being respectively 165° C., 190° C., 195° C., 195° C., 195° C.and 195° C. (die temperature). The extruded strips are subjected tomicrotoming under −100° C., staining with OsO₄ and then observing undera transmission electron microscope.

Example 1

5 kg of carboxylated butadiene-styrene rubber latex having a solidcontent of 50 percent by weight (available from Beijing YanshanPetrochemical Company, Brand: XSBRL-54B1, average particle size of therubber particles in latex: 150 nm) is placed in a vessel, 75 g ofiso-octyl acrylate is added dropwise while stirring, and the stirring iscontinued for 1 hour after the completion of addition. Thereafter, therubber latex is irradiated with Co-60, with the irradiation dose being2.5 Mrad and the irradiation dose rate being 50 Gy/min. The rubberparticles in the irradiated latex have a gel content of 92.6%. A slurryof calcium carbonate (Fine Chemical Factory of Beijing University ofChemical Technology, solid content: 47.3%, average size in one dimensionof the particles: 40 to 60 nm) is compounded with the irradiated latexat a weight ratio of 50:50 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried carboxylated butadiene-styrenerubber/calcium carbonate composite powder 1 is then collected in acyclone.

Example 2

500 kg of calcium carbonate powders (Fine Chemical Factory of BeijingUniversity of Chemical Technology, average size in one dimension of theparticles: 40 to 60 nm) are mixed with 1 kg water in a vessel, theresultant mixture is then dispersed by means of a high-shear dispersingand emulsifying machine to obtain a suspension, which is then compoundedwith the irradiated carboxylated butadiene-styrene rubber latex(prepared as in Example 1) at a weight ratio of 50:50 (on dry basis)while stirring for 1 hour. The mixed latex is spray dried by means of aspray dryer, with the inlet temperature and the outlet temperature being140 to 160° C. and 40 to 60° C., respectively. A dried carboxylatedbutadiene-styrene rubber/calcium carbonate composite powder 2 is thencollected in a cyclone.

Example 3

5 kg of butadiene-styrene rubber latex having a solid content of 45percent by weight (available from Lanzhou Petrochemical Company, Brand:DINGBEN-50, gel content: 88.9%, average particle size of the rubberparticles in latex: 100 nm) is placed in a vessel, 67.5 g of iso-octylacrylate is added dropwise while stirring, and the stirring is continuedfor 1 hour after the completion of addition. Thereafter, the rubberlatex is irradiated with Co-60, with the irradiation dose being 2.5 Mradand the irradiation dose rate being 50 Gy/min. The rubber particles inthe irradiated latex have a gel content of 90.0%. A slurry of calciumcarbonate (as in Example 1) is compounded with the irradiated latex at aweight ratio of 90:10 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried butadiene-styrene rubber/calcium carbonatecomposite powder 1 is then collected in a cyclone.

Example 4

The procedure same as in Example 3 is followed, except that thebutadiene-styrene rubber latex, without irradiation, is directlycompounded with the slurry of calcium carbonate at a weight ratio of80:20 (on dry basis) while stirring for 1 hour. The mixed latex is spraydried by means of a spray dryer, with the inlet temperature and theoutlet temperature being 140 to 160° C. and 40 to 60° C., respectively.A dried butadiene-styrene rubber/calcium carbonate composite powder 2 isthen collected in a cyclone.

Example 5

The procedure same as in Example 3 is followed, except that thebutadiene-styrene rubber latex, without irradiation, is directlycompounded with the slurry of calcium carbonate and an aqueous solutionof sodium benzoate (available from Wuhan Youjishiye Corporation) at aweight ratio of 80:20:10 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried butadiene-styrene rubber/calcium carbonatecomposite powder containing the nucleating agent is then collected in acyclone.

Example 6

Sodium-based montmorillonite (available from Qinghe Factory,Zhangjiakou, Hebei, the particles can be dispersed as flakes of 1 to 20nm thick and 200 to 1000 nm long) is mixed with water in a concentrationof 5 percent by weight, dispersed by means of a high-shear disperser andthen placed for more than one week. After that period, the mixture isdispersed again by means of a high-shear disperser to obtain a stablesuspension, with the layers of sheet montmorillointe being sufficientlyexfoliated. The irradiated butadiene-styrene rubber latex (prepared asin Example 3) is compounded with the above slurry of montmorillonite ata weight ratio of 90:10 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried butadiene-styrene rubber/montmorillonitecomposite powder 1 is then collected in a cyclone.

Example 7

The procedure same as in Example 6 is followed, except that the weightratio of the irradiated butadiene-styrene rubber latex to the slurry ofsodium-based montmorillonite is changed to 99:1 (on dry basis), with adried butadiene-styrene rubber/montmorillonite composite powder 2 beingobtained.

Example 8

Silicon dioxide powders (available from Shenyang Chemical Corporation,average size in one dimension of its particles: 7 to 30 nm) are mixedwith water in a concentration of 5 percent by weight and then dispersedby means of a high-shear disperser to obtain a stable suspension. 5 kgof carboxylated acrylonitrile-butadiene rubber latex having a solidcontent of 45 percent by weight (available from Lanzhou PetrochemicalCompany, Brand: XNBRL, average particle size of the rubber particles inlatex: 50 nm) is placed in a vessel, 67.5 g of iso-octyl acrylate isadded dropwise while stirring, and the stirring is continued for 1 hourafter the completion of addition. Thereafter, the rubber latex isirradiated with Co-60, with the irradiation dose being 2.5 Mrad and theirradiation dose rate being 50 Gy/min. The rubber particles in theirradiated latex have a gel content of 96.1%. The irradiatedacrylonitrile-butadiene rubber latex is compounded with the above slurryof silicon dioxide at a weight ratio of 90:10 (on dry basis) whilestirring for 1 hour. The mixed latex is spray dried by means of a spraydryer, with the inlet temperature and the outlet temperature being 140to 160° C. and 40 to 60° C., respectively. A dried carboxylatedacrylonitrile-butadiene rubber/silicon dioxide composite powder is thencollected in a cyclone.

Example 9

The procedure same as in Example 8 is followed, except that the slurryof silicon dioxide is replaced by the slurry of calcium carbonate (as inExample 1), with a dried carboxylated acrylonitrile/calcium carbonatecomposite powder being obtained.

Example 10

Titanium dioxide powders (available from Beijing University of ChemicalTechnology, average size in one dimension of its particles: 40 to 60 nm)are mixed with water in a concentration of 20 percent by weight and thendispersed by means of a high-shear disperser to obtain a stablesuspension. The irradiated butadiene-styrene rubber latex (prepared asin Example 3) is compounded with the above slurry of titanium dioxide ata weight ratio of 95:5 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried butadiene-styrene rubber/titanium dioxidecomposite powder is then collected in a cyclone.

Example 11

Magnesium hydroxide powders (available from Beijing University ofChemical Technology, average size in one dimension of its particles: 20to 40 nm) is mixed with water in a concentration of 20 percent by weightand then dispersed by means of a high-shear disperser to obtain a stablesuspension. 5 kg of acrylonitrile-butadiene rubber latex having a solidcontent of 45 percent by weight (available from the Latex ReseachCenter, Lanzhou Petrochemical Company, Brand: DINGJING-26, averageparticle size of the rubber particles in latex: 100 nm) is placed in avessel, 112.5 g of trimethylolpropane triacrylate is added dropwisewhile stirring, and the stirring is continued for 1 hour after thecompletion of addition. Thereafter, the rubber latex is irradiated withCo-60, with the irradiation dose being 1.0 Mrad and the irradiation doserate being 50 Gy/min. The rubber particles in the irradiated latex havea gel content of 90.0%. The irradiated acrylonitrile-butadiene rubberlatex is compounded with the above slurry of magnesium hydroxide at aweight ratio of 40:60 (on dry basis) while stirring for 1 hour. Themixed latex is spray dried by means of a spray dryer, with the inlettemperature and the outlet temperature being 140 to 160° C. and 40 to60° C., respectively. A dried acrylonitrile-butadiene rubber/magnesiumhydroxide composite powder is then collected in a cyclone.

Example 12

5 kg of butadiene-styrene-vinylpyridine rubber latex having a solidcontent of 40 percent by weight (available from Changzhihai LatexCompany, Cixi, Zhejiang, Brand: 55555, average particle size of therubber particles in latex: 100 nm) is placed in a vessel, 100 g oftrimethylolpropane triacrylate is added dropwise while stirring, and thestirring is continued for 1 hour after the completion of addition.Thereafter, the rubber latex is irradiated with Co-60, with theirradiation dose being 2.5 Mrad and the irradiation dose rate being 50Gy/min. The rubber particles in the irradiated latex have a gel contentof 87.0%. The irradiated rubber latex is compounded with the slurry ofmontmorillonite (prepared as in Example 6) at a weight ratio of 95:5 (ondry basis) while stirring for 1 hour. The mixed latex is spray dried bymeans of a spray dryer, with the inlet temperature and the outlettemperature being 140 to 160° C. and 40 to 60° C., respectively. A driedbutadiene-styrene-vinylpyridine rubber/montmorillonite composite powderis then collected in a cyclone.

Example 13

50 g of metallic silver powders (Zhengyuan Nanomaterial EngineeringCompany, Shangdong, average size: 20 to 80 nm) are mixed with 1 kg waterin a vessel and then dispersed in a high-shear dispersing andemulsifying machine to obtain a suspension. The resultant suspension iscompounded with the irradiated carboxylated butadiene-styrene rubberlatex (prepared as in Example 1) at a weight ratio of 1:99 (on drybasis) while stirring for 1 hour. The mixed latex is spray dried bymeans of a spray dryer, with the inlet temperature and the outlettemperature being 140 to 160° C. and 40 to 60° C., respectively. A driedcarboxylated butadiene-styrene rubber/metallic silver composite powderis then collected in a cyclone.

Example 14

The butadiene-styrene-vinylpyridine rubber/montmorillointe compositepowder prepared as in Example 12 is compounded with Nylon 6 (availablefrom UBE, Japan, Brand: 1013B) and antioxidant Irganox 1010 (availablefrom Ciba-Geigy, Switzerland) at a weight ratio of Nylon 6:the compositepowder:1010 of 100:15:0.3. The blending and pelleting are carried out ina ZSK-25 twin-screw extruder (Werner & Pfleiderer Co., Germany), withthe temperatures for each section of the extruder being respectively220° C., 235° C., 235° C., 235° C., 235° C. and 235° C. (dietemperature). The extruded pellets are injection-molded into standardtest bars and then subjected to various tests of mechanical properties.The results are listed in Table 1. FIG. 3 is the micrograph of thesample.

Comparative Example 1

The nylon pellets as in Example 14 are compounded with a powderybutadiene-styrene-vinylpyridine rubber (obtained by directly spraydrying the irradiated butadiene-styrene-vinylpyridine rubber latex as inExample 12, without mixing the slurry of montmorillonite) andantioxidant Irganox 1010 at a weight ratio of nylon:powderybutadiene-styrene-vinylpyridine rubber:1010 of 100:15:0.3. Standard testbars are obtained by extruding and injection-molding as in Example 14and then subjected to various tests of mechanical properties. Theresults are listed in Table 1.

Comparative Example 2

The procedure as in Example 14 is followed, except that no compositepowder is used. Standard test bars are obtained by extruding andinjection-molding as in Example 14 and then subjected to various testsof mechanical properties. The results are listed in Table 1.

Example 15

The butadiene-styrene rubber/calcium carbonate composite powdercontaining a nucleating agent prepared as in Example 5 is compoundedwith polypropylene pellets (available from Luoyang PetrochemicalCompany, Brand: B-200, melt index: 0.35 g/10 min) and antioxidantIrganox 1010 (available from Ciba-Geigy, Switzerland) at a weight ratioof polypropylene:the composite powder of 100:10, with the amount of theantioxidant being 0.25 part by weight per 100 parts by weight of thetotal weight of polypropylene and the composite powder, the resultantmixture is mixed for 1 minute in a high speed stirrer. The blending andpelleting are carried out in a ZSK-25 twin-screw extruder (Werner &Pfleiderer Co., Germany), with the temperatures for each section of theextruder being respectively 165° C., 190° C., 195° C., 195° C., 195° C.and 195° C. (die temperature). The extruded pellets are injection-moldedinto standard test bars and then subjected to various tests ofmechanical properties. The results are listed in Table 1. FIG. 1 is themicrograph of the sample.

Comparative Example 3

The procedure as in Example 15 is followed, except that no compositepowder is used and that polypropylene is compounded with the antioxidantat a weight ratio of 100:0.25. The extruded pellets are injection-moldedinto standard test bars and then subjected to various tests ofmechanical properties. The results are listed in Table 1.

Comparative Example 4

The procedure as in Example 15 is followed, except that thebutadiene-styrene rubber/calcium carbonate composite powder containing anucleating agent is replaced by a powdery butadiene-styrene rubbercontaining sodium benzoate (prepared by adding 45 g of sodium benzoateto 1 kg of the butadiene-styrene rubber latex as in Example 3 whilestirring, continuing the stirring for 1 hour, spray drying the resultantmixed latex by means of a spray dryer, with the inlet temperature andthe outlet temperature being 125 to 145° C. and 45 to 60° C.,respectively, and then collecting the dried butadiene-styrenerubber/sodium benzoate composite powder in a cyclone, the weight ratioof the butadiene-styrene rubber to sodium benzoate in the powder:100:10). The extruded pellets are injection-molded into standard testbars and then subjected to various tests of mechanical properties. Theresults are listed in Table 1.

TABLE 1 Heat Tensile Elongation Izod notched Izod notched FlexuralFlexural distortion strength at break impact strength impact strengthstrength modulus temperature No. (MPa) (%) (J/m)23° C. (J/m)−20° C.(MPa) (GPa) (° C.)1.8 MPa Ex. 14 60.8 25 116 90.1 85.7 2.01 69.2 Comp.56.2 40 107 61.5 79.8 1.83 66.5 Ex. 1 Comp. 82.4 16 34.4 29.8 111 2.4167.4 Ex. 2 Ex. 15 34.6 120 221 31.5 36.0 1.57 116.4 Comp. 36.5 145 64.426.2 36.2 1.54 106.8 Ex. 3 Comp. 33.9 119 186 — 35.9 1.53 116.0 Ex. 4Testing GB 1040 GB 1040 GB 1843 GB 1843 GB 9341 GB 9341 GB 1634 Standard

Example 16

Polypropylene (Daqing Huake Corporation, propylene homopolymer pellets,melt index: 0.4 g/10 min) is intimately mixed with the butadiene-styrenerubber/calcium carbonate composite powder 2 prepared as in Example 4 ata weight ratio of 50:50 in a high speed mixer. The blending andpelleting are carried out in a ZSK-25 twin-screw extruder (Werner &Pfleiderer Co., Germany), with the temperatures for each section of theextruder being respectively 170° C., 190° C., 200° C., 210° C., 220° C.and 210° C. (die temperature). The extruded pellets of the fullyvulcanized thermoplastic elastomer are injection-molded into standardtest bars and then subjected to various tests of mechanical properties.The results are listed in Table 2.

Comparative Example 5

The procedure as in Example 16 is followed, except that thebutadiene-styrene rubber/calcium carbonate composite powder 2 isreplaced by a powdery butadiene-styrene rubber (obtained by directlyspray drying the irradiated butadiene-styrene rubber latex as in Example3, without mixing the slurry of calcium carbonate). The extruded pelletsof the fully vulcanized thermoplastic elastomer are injection-moldedinto standard test bars and then subjected to various tests ofmechanical properties. The results are listed in Table 2.

TABLE 2 Permanent compression Shore Tensile strength deformation Samplehardness (HD) at break (MPa) (22 hrs, 23° C.), % Comp. Ex. 5 49 16.415.8 Ex. 16 48 19.6 16.0

Example 17

28.8 g of epoxy resin prepolymer (Wuxi Resin Factory, Brand: E-44),51.84 g of Premix 1 (prepared as follows) and 54 g ofmethyl-tetrahydrophthalic anhydride (Oriental Chemical Factory, Jiaxing,Zhejiang) are weighted into a three-necked flask, heated by athermostatic water bath at 90° C. and then mixed while stirring for 30minutes. To the resultant mixture is added 0.36 g of triethanolamine(analytic pure, available from Beijing Yili Fine Chemicals), and themixture is evacuated while stirring for 5 minutes and then is cast to apolytetrafluoroethylene mold preheated to 130° C. The mixture isprecured at 130° C. for 1 hour, cooled for mold release and then ispostcured at 110° C. for 16 hours, thereby obtaining a cured product,which is then cut to pieces for determination of various properties. Theresults are listed in table 3. FIG. 2 is the micrograph of the sample.

Preparation of Premix 1:

20 parts by weight of the carboxylated acrylonitrile-butadienerubber/calcium carbonate composite powder (prepared as follows) aremixed with 100 parts by weight of epoxy resin prepolymer (same as above)and the resultant mixture is milled three times by means of a three-rollmill, thereby obtaining Premix 1. Preparation of the carboxylatedacrylonitrile-butadiene rubber/calcium carbonate composite powder:

The irradiated carboxylated acrylonitrile-butadiene rubber latex(prepared by irradiating the carboxylated acrylonitrile-butadiene rubberlatex as in Example 8 in an irradiation dose of 1 Mrad in the presenceof 5 percent by weight of trimethylolpropane triacrylate, based on thedry weight of the carboxylated acrylonitrile-butadiene rubber latex,with the gel content of rubber particles in the irradiated latex being90.0%) is compounded with a suspension of nano-calcium carbonate(prepared by dispersing 100 parts by weight of nano-calcium carbonatecake (available from Beijing Nanuotaike Nanotech Company, Brand: 113-SH,solid content: 50 percent by weight, average size in one dimension ofits particles: 40 to 60 nm) in 400 parts by weight of water in ahigh-shear dispersing and emulsifying machine) at a weight ratio of80:20 (on dry weight), while stirring. The mixed latex is then spraydried to obtain the carboxylated acrylonitrile-butadiene rubber/calciumcarbonate composite powder, with the inlet temperature and outlettemperature being 140 to 160° C. and 40 to 60° C., respectively.

Comparative Example 6

72 g of epoxy resin prepolymer (as in Example 17) and 54 g ofmethyl-tetrahydrophthalic anhydride (as in Example 17) are weighted intoa three-necked flask, heated by a thermostatic water bath at 90° C. andthen mixed while stirring for 30 minutes. To the resultant mixture isadded 0.36 g of triethanolamine (as in Example 17), and the mixture isevacuated while stirring for 5 minutes and then is cast to apolytetrafluoroethylene mold preheated to 130° C. The mixture isprecured at 130° C. for 1 hour, cooled for mold release and then ispostcured at 110° C. for 16 hours, thereby obtaining a cured product,which is then cut to pieces for determination of various properties. Theresults are listed in table 3.

Comparative Example 7

The procedure as in Example 17 is followed, except that Premix 1 isreplaced by Premix 2 (prepared as follows). Various properties aredetermined and the results are listed in table 3.

Preparation of Premix 2:

The irradiated carboxylated acrylonitrile-butadiene rubber latex(prepared by irradiating the carboxylated acrylonitrile-butadiene rubberlatex as in Example 8 in an irradiation dose of 1 Mrad in the presenceof 5 percent by weight of trimethylolpropane triacrylate, based on thedry weight of the carboxylated acrylonitrile-butadiene rubber latex) isspray dried to obtain the powdery carboxylated acrylonitrile-butadienerubber having a gel content of 90.0% and an average particle size of 90nm, with the inlet temperature and outlet temperature being 140 to 160°C. and 40 to 60° C., respectively. 20 parts by weight of the powderycarboxylated acrylonitrile-butadiene rubber are mixed with 100 parts byweight of epoxy resin prepolymer (as in Example 17) and the resultantmixture is milled three times by means of a three-roll mill, therebyobtaining Premix 2.

Comparative Example 8

The procedure as in Example 17 is followed, except that the amount ofthe epoxy resin prepolymer (as in Example 17) is changed into 50.4 g,Premix 1 is replaced by 30.24 g of Premix 3 (prepared as follows).Various properties are determined and the results are listed in table 3.

Preparation of Premix 3:

40 parts by weight of nano-calcium carbonate (Fine Chemical Factory ofBeijing University of Chemical Technology, average size in one dimensionof its particles: 40 to 60 nm) are mixed with 100 parts by weight ofepoxy resin prepolymer (as in Example 17) and the resultant mixture ismilled three times by means of a three-roll mill, thereby obtainingPremix 3.

Comparative Example 9

The procedure as in Example 17 is followed, except that 33.12 g of theepoxy resin prepolymer (as in Example 17), 41.5 g of Premix 2 (as inComparative Example 7) and 6.02 g of Premix 3 (as in Comparative Example8) are mixed. Various properties are determined and the results arelisted in table 3.

TABLE 3 Weight ratio of Impact Flexural Flexural toughener: strengthstrength modulus Heat distortion resin (kJ/m²) (MPa) (GPa) temerpature(°C.) Tg(° C.) Ex. 17 12:100 28.2 97.7 2.73 104.7 111.7(DSC) Comp.  0:10011.8 104 3.13 101.3 105.8(DSC) Ex. 6 Comp. 12:100 21.4 94.5 2.56 104.9113.1(DSC) Ex. 7 Comp. 12:100 11.6 87.1 3.32 101.8 107.7(DSC) Ex. 8Comp. 12:100 20.1 91.9 2.71 102.9 111.2(DSC) Ex. 9

The invention claimed is:
 1. A process for preparing a composite powdercomprising rubber particles having a cross-linked structure and ahomogeneous structure and inorganic particles distributed between saidrubber particles, comprising: a. intimately mixing a slurry of inorganicparticles with a cross-linked synthetic rubber latex to obtain a mixedlatex and then drying the mixed latex; or b. vulcanizing a rubber latexby high-energy irradiation in the absence or presence of a cross-linkingagent, intimately mixing a slurry of inorganic particles with theirradiated rubber latex to obtain a mixed latex and then drying themixed latex.
 2. The process according to claim 1, wherein the slurry ofinorganic particles is an aqueous suspension of inorganic particles. 3.The process according to claim 1, wherein said inorganic particles havean average size of 0.2 to 500 nm in at least one dimension and areselected from the group consisting of elemental metals or alloysthereof; metal oxides; metal or non-metal nitrides; non-metal carbides;non-metal oxides; metal hydroxides; metal salts; mineral earths; and themixtures of two or more of them; and wherein the weight ratio of therubber particles contained in said rubber latex to the inorganicparticles contained in said slurry is from 99.5:0.5 to 20:80.
 4. Theprocess according to claim 3, wherein the weight ratio of the rubberparticles contained in said rubber latex to the inorganic particlescontained in said slurry is from 99:1 to 50:50.
 5. The process accordingto claim 1, wherein the step of intimately mixing a slurry of inorganicparticles to obtain said mixed latex in steps a or b further comprisesadding an aqueous solution of water-soluble nucleating agents forplastics in a weight ratio of the rubber particles contained in saidlatex to the nucleating agent contained in said aqueous solution of 99:1to 50:50.
 6. The process according to claim 5, wherein said nucleatingagent is sodium benzoate.
 7. The process according to claim 5, whereinthe weight ratio of the rubber particles contained in said latex to thenucleating agent contained in said aqueous solution of 97:3 to 70:30. 8.The process according to claim 3, wherein said inorganic particles havean average size of 0.5 to 100 nm in at least one dimension.
 9. Theprocess according to claim 3, wherein said inorganic particles areselected from the group consisting of gold, silver, copper, iron, goldalloys, silver alloys, copper alloys, iron alloys, aluminum oxide,magnesium oxide, titanium dioxide, iron sesquioxide, ferroferric oxide,silver oxide, zinc oxide, aluminum nitride, silicon nitride, siliconcarbide, silicon dioxide, aluminum hydroxide, magnesium hydroxide,calcium carbonate, barium sulfate, calcium sulfate, silver chloride,asbestos, talc, kaolin, mica, feldspar, wollastonite, montmorillonite,and the mixtures of two or more of them.
 10. The process according toclaim 1, wherein said cross-linked synthetic rubber latexes used in stepa. have a gel content of 80 percent by weight or more.
 11. The processaccording to claim 1, wherein said cross-linked synthetic rubber latexesused in step a. are selected from the group consisting of cross-linkedstyrene-butadiene latex, cross-linked carboxylated styrene-butadienelatex, cross-linked polybutadiene latex, cross-linkedacrylonitrile-butadiene latex, cross-linked carboxylatedacrylonitrile-butadiene latex, cross-linked neoprene latex andcross-linked acrylic latex.
 12. The process according to claim 1,wherein said rubber latexes used in step b. are selected from the groupconsisting of natural rubber latex, styrene-butadiene rubber latex,carboxylated styrene-butadiene rubber latex, acrylonitrile-butadienerubber latex, carboxylated acrylonitrile-butadiene rubber latex,polybutadiene rubber latex, neoprene rubber latex, silicone rubberlatex, acrylic rubber latex, butadiene-styrene-vinylpyridine rubberlatex, isoprene rubber latex, butyl rubber latex, ethylene-proplyenerubber latex, polysulfide rubber latex, acrylate-butadiene rubber latex,urethane rubber latex, and fluorine rubber latex.